WO1996017020A1 - Melanges multifonctionnels d'ester de cyanate et d'epoxydes - Google Patents

Melanges multifonctionnels d'ester de cyanate et d'epoxydes Download PDF

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Publication number
WO1996017020A1
WO1996017020A1 PCT/US1995/014560 US9514560W WO9617020A1 WO 1996017020 A1 WO1996017020 A1 WO 1996017020A1 US 9514560 W US9514560 W US 9514560W WO 9617020 A1 WO9617020 A1 WO 9617020A1
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WIPO (PCT)
Prior art keywords
blend
percent
phenolic
copolymer
epoxy resin
Prior art date
Application number
PCT/US1995/014560
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English (en)
Inventor
Sajal Das
Geraldine Shu-Chuin Su
Original Assignee
Alliedsignal Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to HU9801441A priority Critical patent/HU221408B1/hu
Priority to EP95939853A priority patent/EP0794979B1/fr
Priority to JP51881396A priority patent/JP3735119B2/ja
Priority to AU41517/96A priority patent/AU695822B2/en
Priority to MX9704022A priority patent/MX9704022A/es
Priority to CZ19971618A priority patent/CZ290172B6/cs
Priority to PL95320741A priority patent/PL186082B1/pl
Priority to BR9509932A priority patent/BR9509932A/pt
Application filed by Alliedsignal Inc. filed Critical Alliedsignal Inc.
Priority to DE69504702T priority patent/DE69504702T2/de
Priority to CA002205811A priority patent/CA2205811C/fr
Priority to DK95939853T priority patent/DK0794979T3/da
Publication of WO1996017020A1 publication Critical patent/WO1996017020A1/fr
Priority to NO19972462A priority patent/NO311036B1/no
Priority to HK98101855A priority patent/HK1002866A1/xx

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/10—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/26—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/02—Disazo dyes
    • C09B33/147—Disazo dyes in which the coupling component is a bis -(-o-hydroxy-carboxylic- acid amide)
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0675—Azo dyes
    • G03G5/0679—Disazo dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0675—Azo dyes
    • G03G5/0679—Disazo dyes
    • G03G5/0681—Disazo dyes containing hetero rings in the part of the molecule between the azo-groups
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/901—Printed circuit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y10T428/31522—Next to metal

Definitions

  • the invention relates to certain novel blends of phenolic cyanate-phenolic triazine copolymers and epoxy resins, as well as to articles prepared from said blends. More particularly, the invention relates to such blends which have improved properties.
  • Phenolic resins are a class of synthetic materials which greatly vary in molecular structure. Therefore, a multitude of applications for these products exists as a result of the array of physical properties that arise from the synthetic options.
  • phenolics disadvantageously exhibit less than desirable thermal oxidative stability and produce an extensive, uncontrollable amount of volatile by ⁇ products during cross-linking.
  • U.S. In order to obviate certain of the disadvantages attendant to phenolics, U.S.
  • Patent No. 4,970,276 proposed a modified multifunctional phenolic cyanate/phenolic triazine copolymer ("PT resin") which had greater oxidative, mechanical, and thermal stability as compared to conventional phenolic resins, and did not produce volatile by-products during crosslinking. Further, these PT resins possessed better elongation properties and higher glass transition temperatures than the conventional phenolic resins. Additional examples of such PT resins are described in U.S. Patent Nos. 4,970,276, 4,978,727, and 5,126,412.
  • thermosettable blends having improved mechanical properties
  • dicyanate esters with epoxy resins as disclosed in U.S. Patent Nos. 4,612,359, 4,506,603, 4,477,629, 4,546,131, 4,487,915, and 3,562,214, and in Shimp, et al., "Co-Reaction of Epoxide and Cyanate Resins," 33rd Int'l SAMPE Symposium and Exhibition 1 - 13 (Calif. March 7 - 10, 1988) and Shimp, AroCy* Cyanate Ester Resins Chemistry, Properties & Applications, (3rd Ed. May, 1991).
  • These blends have been useful in the production of base materials for printed circuits as disclosed in Patent Nos. DE 4,022,255, DD 290,844, DE 4,125,420, and DE 4,224,835.
  • thermosettable resin blends which, when cured, possess excellent thermal stability and mechanical properties, there is room for additional improvement in the overall mechanical properties, especially in glass transition temperature, as well as in water absorption.
  • thermosettable resin blend which, when cured, is superior to prior art phenolic resins and dicyanate blends in one or more of the properties selected from glass transition temperature, flexural strength, flexural modulus, elongation, and water absorption.
  • a blend comprising: a) a multifunctional phenolic cyanate/phenolic triazine copolymer
  • n is a positive whole number equal to or greater than 1
  • q and r are the same or different at each occurrence and are whole numbers from 0 to 3 with the proviso that the sum of q and r at each occurrence is equal to 3
  • o and p are the same or different at each occurrence and are whole numbers from 0 to 4, with the proviso that the sum of o and p is equal to 4;
  • -X- is a divalent organic radical
  • R 3 is the same or different at each occurrence and is a substituent other than hydrogen which is unreactive under conditions necessary to completely cure the copolymer; and b) an epoxy resin.
  • Another aspect of the invention pertains to the article resulting from curing the aforementioned blend with a curing quantity of a curing agent, catalyst or mixture of curing agent and catalyst therefor.
  • the blend of the invention and the products resulting therefrom exhibit one or more beneficial properties, such as, improved glass transition temperature and water absorption.
  • Component a of the present invention includes multifunctional phenolic cyanate/phenolic triazine copolymer resins or "PT resins" having at least three phenolic moieties of the formula I linked by at least one of said open valences to one or more triazine moieties of the formula II.
  • the remainder of said open valences being substituted with -OCN, -OH or other triazine moieties, provided that at least one of said remaining open valences is substituted with a -OCN group, wherein R 3 , n, q, r, o, p, and X are as described above.
  • R 3 is an inert substituent.
  • suitable R 3 groups are such inert substituents as halo, trihalomethyl, alkyl, alkoxy, phenyl, and the like.
  • -X- is a divalent organic radical.
  • suitable -X- groups are alkylene such as methylene, ethylmethylene, 2- ethylpentylmethylene, methylmethylene, isopropylmethylene, isobutylmethylene, pentylmethylene, furylmethylene, and the like; arylenes such as 1,3- benzenedimethylene, phenylmethylene, 1,4-benzenedimethylene, 2,2-bis-(4- phenylene)propane, 4,4-diphenylene dimethylenethane and the like; and cycloalkylenes such as cyclohexylene, cyclooctylene, 1,3-cyclohexanedimethylene, and the like.
  • -X- is a substituted or unsubstituted methylene or 1,4-benzenedimethylene wherein permissible substituents are alkyl or furyl;
  • q and r are the same or different at each occurrence and are positive whole numbers from 0 to 3, with the proviso that the sum of q and r is 3;
  • R 3 is alkyl; n is from 1 to about 20; and o and p are the same or different at each occurrence and are positive whole numbers from 0 to 4, with the proviso that the sum of o and p is 4; wherein up to about 30 mol percent of the phenyl moieties of said copolymer are substituted with said triazine moieties, up to about 90 mol percent of said phenyl moieties are substituted with -OH groups and up to about 90 mol percent of said phenyl moieties are substituted with -OCN groups, said mol percent being based on the total mols of phenyl groups in said copolymer. Unless indicated otherwise, all references herein are in terms of weight percent.
  • phenyl groups of the PT resin are substituted with triazine moieties, from about 40 to about 90 mol percent of said phenyl groups are substituted with -OCN groups and from about 2 to about 50 mol percent of said phenyl groups are substituted with -OH groups, said mol percent based on the total mols of phenyl group in said copolymer;
  • -X- is methylene, methylene substituted with alkyl having from about 1 to about 10 carbon atoms, halo or furfuryl, or xylene;
  • R 3 is methyl or ethyl; o is 0 or 1; n is from about 1 to about 10; q is 0 or 1; r is 2 or 3; p is 3 or 4.
  • n is 3 to about 10; from about 5 to about 20 mol percent of the phenyl groups of the phenyl triazine/phenyl cyanate copolymer are substituted with -OCN groups and from about 5 to about 20 mol percent of said phenyl groups are substituted with -OH groups, said mol percent being based on the total mols of phenyl groups in said copolymer; q is 0;
  • copolymers are preferably linear copolymers having recurring units of the formula HI:
  • R 3 , o, p, q, r, -X-, and n are as described above and wherein:
  • Z j is -OH or -OCN at each occurrence;
  • Z ⁇ is a trivalent triazine moiety; with the proviso that from about 10 to about 20 mol percent of the phenyl groups of the copolymer are substituted with trivalent triazine moieties, from about 70 to about 75 mol percent of phenyl groups are substituted with -OCN groups, and from about 10 to about 20 mol percent of the phenyl groups are substituted with -OH groups, said mol percent based on the total mols of phenyl groups in the copolymer.
  • Suitable materials which can be employed in the preparation of the phenolic cyanate resin precursor to the PT resin of component a include phenolic salts of formula IV:
  • R 3 , q, r, o, p, n, and X are as described above, and V is hydrogen or a cation of an organic or inorganic base which is formed by reaction between said base and the protons of a phenol to form the corresponding basic salt, wherein the mol ratio of cations to hydrogen are sufficient to form the desired mol percent of - OCN groups in the desired phenolic cyanate.
  • PT resins suitable for use in component a of the blend of the present invention may be prepared by the known method of controlled "polycyclotrimerization" of the phenolic cyanate precursor having formula V:
  • Suitable epoxy resins for blending with the PT resin include bisphenol A based epoxy resins, halogenated epoxy resins, epoxy novolac resins, polyglycol epoxy resins, and mixtures and copolymers thereof.
  • suitable bisphenol A based epoxy resins include compounds of the following formula:
  • CH wherein the average value of m is from about 0J to about 1, preferably about OJ to about 0.2.
  • Suitable epoxy novolac resins include compounds of the following formula:
  • Suitable halogenated epoxy resins include those epoxies substituted with chlorine, bromine, fluorine, and mixtures thereof. Illustrations of suitable brominated epoxy resins include compounds of the following formula:
  • epoxy resins can be obtained from commercial sources, e.g., from The Dow Chemical Company.
  • suitable epoxy resins include multifunctional epoxy resins, such as tetra- and tri-functional epoxy resins, which may be used alone, or mixed or copolymerized with the above-described epoxy resins.
  • multifunctional epoxy resin means a resin which may contain greater than about 1 to about 4, preferably 3 to about 4 epoxy groups, more preferably 4 epoxy groups. Illustrations of such tetra-functional and tri-functional multifunctional epoxy resins are
  • an epoxy having, based upon the total weight of the epoxy resin, from about 15 percent to about 45 percent, preferably about 8 percent to about 12 percent, bromination is employed. Unless indicated otherwise, all references herein are with respect to weight percent. As the amount of brominated epoxy resin in the blend of the present invention is increased, various properties, such as adhesion and glass transition temperature (“T g ”) also increase.
  • T g adhesion and glass transition temperature
  • the blend of the present invention includes a mixture of, based upon the total weight of the blend, from about 5 to about 95 percent, preferably from about 15 to about 50 percent, and more preferably about 25 to about 30 percent PT resin with from about 5 to about 95 percent, preferably about 25 to about 70 percent, epoxy resin.
  • the blend of the present invention may optionally contain, based upon the total weight of the blend, from about 0 to about 20, preferably about 3 to about 10 percent, of a multifunctional epoxy resin in addition to the amount of epoxy resin or resins employed in component b. Examples of suitable multifunctional epoxy resins include those described above. When a blend having high T g and adhesion properties is desired, it is preferred that such multifunctional epoxy resins are used as a third component in the blend of the present invention.
  • the blend of the present invention may also optionally contain a catalyst for the purpose of increasing the cure rate of the blend.
  • the blend of the present invention contains, based upon the total weight of the blend, from about 0.01 percent to about 0.2 percent, preferably 0.08 percent to about 0J1 percent of a catalyst.
  • Suitable catalysts employed herein are the primary catalysts and/or the organic catalysts or "curing agents". Illustrations of the primary catalysts include, for example, transition metal salts of aliphatic and aromatic carboxylic acids, nitrogen and phosphorus compounds. Particularly suitable catalysts include, for example, lead naphthenate, manganese naphthenate, manganese octoate, manganic acetylacetonate, cobalt octoate, cobalt naphthenate, cobalt acetylacetonate, zinc octoate, zinc naphthenate, zinc acetylacetonate, copper acetylacetonate, cupric naphthenate, nickel acetylacetonate, titanyl acetylacetonate, ferric octoate, tin octoate, diazabicylo[2.2.2]octane, catechol, lJ-dimethyl-3-phenylurea, mixtures thereof
  • Suitable catalysts include organic catalysts or curing agents, such as alkyl phenols, imidazoles and mixtures thereof. These organic catalysts or curing agents are employed for the purpose of further accelerating the cure, and may be used alone or in combination with the above-mentioned metal catalysts.
  • Preferable organic catalysts may be selected from the group consisting of nonylphenol, 1-methyl-imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole,
  • 2-methylimidazole (“2-MI”)
  • 2-MI 2-methylimidazole
  • 0.07% 2-MI may be employed.
  • the blend i.e., the PT resin and/or epoxy resin component
  • the blend can be blended with other compounds, such as solvents, fillers, mold release agents, pigments, dyes, flow modifiers, combinations thereof and the like. Examples of such compounds are described in U.S. Patent No. 4,496,695, which is incorporated herein by reference.
  • Suitable such solvents include, for example, aromatic hydrocarbons, ketones, halogenated hydrocarbons, combinations thereof and the like.
  • Particularly suitable solvents include, for example, dimethylformamide, tetrahydrofuran, acetone, l-methyl-2-pyrrolidinone, methylethylketone, methylene chloride, combinations thereof and the like.
  • the PT resin and/or epoxy resin may contain fillers for use in where the structural strength and integrity of a structure has to be maintained, and for other purposes known to those of skill in the art.
  • Any suitable filler known to those of skill in the art may be used.
  • Such fillers may be selected from a wide variety of organic and inorganic materials such as polymers, minerals, metals, metal oxides, siliceous materials, and metal salts.
  • Illustrative of useful fillers are kevlar fibers, rock-wool, slag wool, fiberglass, phenolic fibers, aramide, boron, and carbon fibers,
  • thermoplastic polymers as for example, polyesters, polyimides, polyamides, polysulfones, polyaramids, polyester carbonates, polyphenylene ether, polyethersulfones, polyethylene, polypropylene, polycarbonates, polyetherimides, polysulfides, polyacrylates, polyvinyls and the like.
  • Methods for producing reinforced and/or filled blends include melt blending, extrusion and molding processes, simple mixing and dispersion of both materials in suitable medium by methods known in the art.
  • a curable resin blend of this invention may include white pigments such as titanium dioxide, and coloring pigments or various organic dyes and pigments, such as lead yellow, carbon black, iron black, molybdenium red, prussian blue, navy blue, cadmium yellow, and cadmium red.
  • white pigments such as titanium dioxide
  • coloring pigments or various organic dyes and pigments such as lead yellow, carbon black, iron black, molybdenium red, prussian blue, navy blue, cadmium yellow, and cadmium red.
  • the curable resin blends of the present invention may be prepared by either a wet process or a dry process, both of which are conventionally known in the art. Choice of the process is determined by the proportion of components and final use of the blend.
  • each component is individually dissolved in a solvent, then all of the components are blended so as to obtain a curable resin blend
  • the components 15 having the desired proportion.
  • at least one of the components is dissolved in a solvent, and the other components are added thereto.
  • at least these two components are initially dissolved in a solvent before other components are added thereto.
  • the blends prepared according to the wet process contain a solvent or solvents. The solvent may be removed by heating the blend or by keeping the blend under a reduced pressure.
  • Solvents suitable for dissolving the components employed in the wet process include, for example, ketones, such as acetone, methyl ethyl ketone, and the like, as well as tetrahydrofuran, methylene chloride, dimethylformamide, l-methyl-2- pyrrolidinone, and the like.
  • the PT resin and epoxy resin components are continuously mixed via conventional means at temperatures of about 65°C to about 75°C until homogeneous.
  • An effective amount of a solution comprised of from about 15 to about 25 percent, based upon the total weight of the solution, of catalyst predissolved in an alkyl phenol solvent, such as nonylphenol, dodecylphenol, o-cresol, 2-sec-butylphenol and 2,6-dinonylphenol, most preferably nonylphenol, may optionally be added thereto such that the amount of catalyst in the homogeneously blended blend is from about 0.06 to about 0.07 percent, based
  • the method of curing the resin blend of this invention is not restricted in particular. Usually it is performed by heating. Generally a temperature of about 18°C to about 400°C, preferably a temperature of about 100°C to about 300°C, is selected.
  • the time required for curing differs depending upon the form in which the resin blend of this invention is used, i.e., depending on whether it is a thin film, or a relatively thick molded article or laminate. Usually, a period sufficient for curing the resin may be selected from the range of from about 1 hour to about 2 hours.
  • the resin blend of this invention is to be used in molded articles, such as those produced via resin transfer molding, compression molding, injection molding, and the like, laminates or bonded structures, it is desirable to apply pressure during the heat curing mentioned above.
  • the resin blend of this invention may contain up to 5 percent, based upon the total weight of the blend, of a known photosensitizer, for example, an organic carbonyl compound such as benzoin,
  • Such a photocurable resin blend containing a photosensitizer is effective in coating applications.
  • the blends of the present invention are preferably employed to prepare articles including, but not limited to, composites and laminates, i.e., electrical laminates such as printed circuit boards or rigid substances suitable for the production of printed circuit boards.
  • one or more plies, preferably about 4 to about 8 plies, of a fibrous substrate are coated and/or impregnated with the blend of the present invention and laminated.
  • the substrate is cured at a temperature of about 100°C to about 300°C for about 1 hour to about 2 hours to form a rigid substrate.
  • the blends can be used to coat and/or impregnate fibrous substrates such as fiberglass, nylon, paper such as that obtainable from DuPont under the tradename "Thermount”, polyimides, graphite, and the like.
  • the substrate can be in the form of woven fabric, mat, monofilament, multifilament rovings, and the like.
  • the ratio of the blend of the present invention to the substrate in a prepreg may vary from, based upon the total weight of the preimpregnated substrate or "prepreg", about 20:80 to about 50:50, and preferably from about 35:65 to about
  • prepreg shall refer to the substrate coated with the uncured resin blend of the present invention.
  • At least one ply preferably 1 to about 2
  • 18 plies, of a sheet of copper or other electrically conductive material, e.g., gold, silver, aluminum and the like, can then be laminated to the rigid substrate using laminating conditions such as pressure of about 0.34 MPa to about 2.76 MPa and temperatures of about 50°C to about 300°C applied for about 30 to about 300 minutes. Then a circuit can be etched into the conductive layer using techniques well-known to form circuit boards.
  • laminating conditions such as pressure of about 0.34 MPa to about 2.76 MPa and temperatures of about 50°C to about 300°C applied for about 30 to about 300 minutes.
  • the following properties of the blends produced in the Examples were determined as follows: a) The glass transition temperatures were determined by using differential scanning calorimetry ("DSC) via the method described in Interconnecting Packaging Circuitry 2.4.25 (1986)("IPC), as well as by using thermal mechanical analysis ('TMA”) via the method described in IPC 2.4.24. b) The flammability was determined via the method described in the
  • Component A is a cyanate ester resin available from AlliedSignal Inc., Morristown, New Jersey under the tradename "Primaset”, having a molecular weight of about 480, a viscosity at 80°C of about 0.3 Pa «S to about 0.35 Pa»S and a gel time of 15 to 20 minutes at 200°C.
  • Component B is a brominated epoxy resin available from The Dow Chemical Company having an epoxide equivalent weight ("EEW) of about 425 to about 440, a bromine content of about 20 percent by weight, and a viscosity at 25°C of about 1.5 Pa « S to about 2.5 Pa «S.
  • Component C is a tetrafunctional epoxy resin available from Shell
  • Component D is a brominated epoxy resin available from The Dow Chemical Company under the tradename "DER 592" having an EEW of about 345 to about 375, a bromine content of about 17 percent by weight, and a viscosity at 171°C of about 0.8 Pa- S.
  • Component E is a tetrafunctional epoxy resin available from Ciba-Geigy Corporation under the tradename "MY-720", having an EEW of about 117 to about 134 and a viscosity at 50°C of about 8 to 18 Pa»S.
  • Component F is an epoxy novolac resin available from The Dow Chemical Company under the tradename 'OEN 431", having an EEW of about 172 to about
  • Component G is a liquid Bisphenol-A type epoxy resin available from The
  • Component H is a catalytic solution of manganese octoate (6 percent active manganese) in mineral spirits available from Pfaltz & Bauer, Inc.
  • Example Comp. Example Example Comp.
  • PT30 resin Component A
  • Component B brominated epoxy resin
  • a catalytic solution of manganese octoate 6% active manganese
  • a glass fabric is then impregnated with the resulting mixture and cured at 177°C with 1.03-138 MPa pressure for 15 minutes, and then for about 1 hour at
  • PT30 resin Component A
  • Component B brominated epoxy resin
  • Component C tetrafunetional epoxy resin
  • Example 3 Substrate Coated With Blend of PT Resin. Epoxy
  • a glass fabric substrate is then impregnated with the resulting blend and cured in the same manner and under the same conditions described in Example 1.
  • Comparative Example 1 About 49.2 parts by weight of a bisphenol A dicyanate ester (BADCY, available from Lonza Ltd.) having a melting point of about 79°C, a viscosity at
  • a glass fabric is then impregnated with the resulting blend mixture and cured at 177°C for 15 minutes with about 1.38 MPa pressure, and then for about 1 hour at 220°C under the same pressure conditions.
  • Comparative Example 2 About 58J parts of bisphenol A dicyanate ester from Comparative Example 1 is dissolved in a mixture of about 54.4 parts by weight of acetone, about 109J parts of brominated epoxy polymeric material (Component B), and about 18.3 parts of tetrafunetional epoxy resin (Component C). About 0.024% by weight of a catalytic solution of manganese octoate (6% active manganese) in mineral spirits and 0.064% of 2-MI by weight is added thereto under room temperature conditions, and the resulting mixture is stirred for about 2 hours until
  • a glass fabric is then impregnated with the resulting blend and cured in the same manner and under the same conditions described in Comparative Example 1.
  • the thermal, electrical, and moisture absorption properties of laminates described in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 are illustrated in Table I-Q.
  • the resulting blend is poured into a 20.3 cm x 17.78 cm x 0.32 cm glass mold preheated to about 80°C, which was pretreated with a silicone release agent available from Chemlease Inc. under the tradename "Chemlease 70", and then the filled mold is degassed in a vacuum oven set at about 70°C to 80°C with about 4000 Pa vacuum pressure (30 torr). After 18 hours of curing at 120°C, the sample is removed from the glass mold and postcured for another 30 minutes at 150°C, 105 minutes at 180°C, 30 minutes at 200°C, followed by 4 hours at 220°C.
  • Example B Blend of PT Resin With Epoxy Novolac Resin About 200 parts of a PT-30 resin (Component A) and about 200 parts of an epoxy novolac resin (Component F) are combined in a 500 ml beaker, which was heated in the same manner and under the same conditions described in Example A. About 0.22 parts of the catalytic solution of Example A was added thereto, then the resulting mixture is degassed and molded in the manner described in Example A. After 18 hours of curing at 120°C, the sample was removed from the glass mold and post cured for another 0.5 hours at 150°C, 2 hours at 180°C, 0.5 hours at 200°C, followed by 4 hours at 220°C.
  • Example C Blend of PT Resin With Bis A Type Epoxy Resin About 174.9 parts of a PT-30 resin (Component A) and about 174.9 parts
  • Example 28 of a bisphenol A type epoxy resin (Component G) are combined in a 500 ml beaker, which is heated in the same manner and under the same conditions described in Example A. About 0.20 parts of the catalytic solution of Example A is added thereto in the manner described in Example A. The resulting mixture is molded and cured in the manner described in Example A.
  • Comparative Example A The PT resin of Example A is replaced with about 47 parts of the bisphenol A dicyanate of Comparative Example 1. Then, 53 parts of a tetrafunetional epoxy resin (Component E) is added thereto according to the method described in Shimp et al., "Co-Reaction of Epoxide and Cyanate Resins",
  • Comparative Example C The PT resin of Example C is replaced with about 57 parts of the bisphenol A dicyanate of Comparative Example 1. Then, 43 parts of an epoxy resin (Component G) is added thereto according to the method described in Shimp,
  • 30 ⁇ DT' refers to heat distortion temperature, which for pu ⁇ oses herein, is comparable to the glass transition temperature ("T g ").
  • T g glass transition temperature

Abstract

Mélange de résines durcissables comportant un copolymère de cyanate phénolique/triazine phénolique et une résine époxyde, et articles fabriqués à partir dudit mélange. Le mélange de résines durcies que présente une température élevée de transition vitreuse, d'excellentes propriétés mécaniques de résistance à la flexion, d'allongement, de module de flexion, de résistance à la compression et de module de compression, et un faible taux d'absorption d'humidité; il convient pour des stratifiés, des revêtements, des composites et des moules, notamment pour des moulages par transfert ou par compression de résine.
PCT/US1995/014560 1994-11-30 1995-11-29 Melanges multifonctionnels d'ester de cyanate et d'epoxydes WO1996017020A1 (fr)

Priority Applications (13)

Application Number Priority Date Filing Date Title
PL95320741A PL186082B1 (pl) 1994-11-30 1995-11-29 Mieszanka wielofunkcyjnych estrów cyjanianowych iżywic epoksydowych oraz sposób wytwarzania ukształtowanego wyrobu, na drodze utwardzania mieszanki wielofunkcyjnych estrów cyjanianowych i żywic epoksydowych
JP51881396A JP3735119B2 (ja) 1994-11-30 1995-11-29 多官能性シアネートエステルとエポキシのブレンド物
AU41517/96A AU695822B2 (en) 1994-11-30 1995-11-29 Multifunctional cyanate ester and epoxy blends
MX9704022A MX9704022A (es) 1994-11-30 1995-11-29 Mezclas multifuncionales de cianato ester y epoxi.
CZ19971618A CZ290172B6 (cs) 1994-11-30 1995-11-29 Směs obsahující vícefunkční kopolymer fenolický kyanát/fenolický triazin a epoxidovou pryskyřici
HU9801441A HU221408B1 (en) 1994-11-30 1995-11-29 Multifunctional cyanate ester and epoxy blends and products and laminates made from this blends
BR9509932A BR9509932A (pt) 1994-11-30 1995-11-29 Mistura de éster de cianato multifuncional e epóxi
EP95939853A EP0794979B1 (fr) 1994-11-30 1995-11-29 Melanges de copolymeres cyanate-triazine et de resines epoxydes
DE69504702T DE69504702T2 (de) 1994-11-30 1995-11-29 Mischungen aus cyanat-triazin copolymeren und epoxidharzen
CA002205811A CA2205811C (fr) 1994-11-30 1995-11-29 Melanges multifonctionnels d'ester de cyanate et d'epoxydes
DK95939853T DK0794979T3 (da) 1994-11-30 1995-11-29 Blandinger af cyanat-triazin-copolymere og epoxyharpikser
NO19972462A NO311036B1 (no) 1994-11-30 1997-05-29 Multifunksjonelle cyanatester- og epoksyblandinger, anordning oppnadd ved herding av denne blandingen, og laminat og for-impregnert underlag omfattende samme
HK98101855A HK1002866A1 (en) 1994-11-30 1998-03-06 Blends of cyanate-triazine copolymers and epoxy resins

Applications Claiming Priority (2)

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US08/347,017 US5912308A (en) 1994-11-30 1994-11-30 Multifunctional cyanate ester and epoxy blends
US08/347,017 1994-11-30

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WO1996017020A1 true WO1996017020A1 (fr) 1996-06-06

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AU (1) AU695822B2 (fr)
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DE (1) DE69504702T2 (fr)
DK (1) DK0794979T3 (fr)
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HK (1) HK1002866A1 (fr)
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EP1067406A1 (fr) * 1999-07-01 2001-01-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Matière synthéthique pour substrat d'articles optiques

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US20020010286A1 (en) 2002-01-24
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CN1090204C (zh) 2002-09-04
HU221408B1 (en) 2002-09-28
ZA9510156B (en) 1996-05-30
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CZ161897A3 (en) 1997-09-17
RU2160751C2 (ru) 2000-12-20
US5922448A (en) 1999-07-13
HUT77932A (hu) 1998-11-30
AU4151796A (en) 1996-06-19
ATE170899T1 (de) 1998-09-15
BR9509932A (pt) 1997-09-30
EP0794979B1 (fr) 1998-09-09
JPH10509999A (ja) 1998-09-29
EP0794979A1 (fr) 1997-09-17
DE69504702D1 (de) 1998-10-15
KR100384190B1 (ko) 2003-11-28
CA2205811A1 (fr) 1996-06-06
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PL186082B1 (pl) 2003-10-31
US5912308A (en) 1999-06-15
MX9704022A (es) 1998-02-28
CZ290172B6 (cs) 2002-06-12
TW336246B (en) 1998-07-11
CN1166849A (zh) 1997-12-03
HK1002866A1 (en) 1998-09-25
NO311036B1 (no) 2001-10-01
PL320741A1 (en) 1997-10-27
ES2120779T3 (es) 1998-11-01
DE69504702T2 (de) 1999-05-20
NO972462D0 (no) 1997-05-29
JP3735119B2 (ja) 2006-01-18

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